Hybrid reactor heavy product upgrading method with dispersed catalyst uptake

Abstract

More particularly, the invention concerns the in situ formation of a catalyst for a hydrotreatment process starting from a fixed bed catalyst which captures a dispersed catalyst on its solid support.

1 . A process for the hydrotreatment of a heavy oil feed in at least one reactor containing a fixed bed catalyst composed of an active phase deposited on a solid support, in which a solution containing a dispersed catalyst or a precursor of a dispersed catalyst is continuously introduced into said reactor, the particle size of said dispersed catalyst being in the range 1 nm to 100 μm, said fixed bed catalyst capturing said dispersed catalyst on its solid support. 
     
     
         2 . The process as claimed in  claim 1 , in which the particle size of said dispersed catalyst is in the range 10 nm to 75 μm. 
     
     
         3 . The process as claimed in  claim 1 , in which the feed is selected from feeds constituted by hydrocarbon fractions obtained from a crude oil or from atmospheric distillation of a crude oil or from vacuum distillation of a crude oil, said feeds containing a fraction of at least 80% by weight of molecules having a boiling point of at least 300° C. 
     
     
         4 . The process as claimed in  claim 1 , in which the hydrotreatment process is carried out at an absolute pressure in the range 2 MPa to 38 MPa and at a temperature in the range 300° C. to 550° C., and with an hourly space velocity (HSV) of the volume of feed with respect to the volume of catalyst in the range 0.05 h −1  to 10 h −1 . 
     
     
         5 . The process as claimed in  claim 1 , in which said fixed bed catalyst contains one or more elements from groups 4 to 12 of the periodic table of the elements which are deposited on said solid support. 
     
     
         6 . The process as claimed in  claim 5 , in which said solid support for the fixed bed catalyst is selected from amorphous solids selected from silica, alumina, silica-alumina, titanium dioxide and zeolites, alone or as a mixture. 
     
     
         7 . The process as claimed in  claim 5 , in which the macropore volume of said solid support of the fixed bed catalyst represents in the range 0 to 80% of the total pore volume, the median diameter of the macropores of said solid support of the fixed bed catalyst is in the range 100 nm to 5000 nm, and the specific surface area of said solid support of the fixed bed catalyst is more than 75 m 2 /g. 
     
     
         8 . The process as claimed in  claim 5 , in which said fixed bed catalyst contains at least one metal from group VIB. 
     
     
         9 . The process as claimed in  claim 8 , in which said metal from group VIB is selected from molybdenum and tungsten. 
     
     
         10 . The process as claimed in  claim 8 , in which said metal from group VIB is used in association with at least one metal from group VIII. 
     
     
         11 . The process as claimed in  claim 10 , in which said metal from group VIII is selected from nickel and cobalt. 
     
     
         12 . The process as claimed in  claim 1 , in which said solution containing said dispersed catalyst or said precursor of a dispersed catalyst is introduced continuously with the feed or with a conveying fluid. 
     
     
         13 . The process as claimed in  claim 12 , in which said conveying fluid is selected from aromatic hydrocarbons and vacuum distillates, alone or as a mixture. 
     
     
         14 . The process as claimed in  claim 1 , in which said dispersed catalyst or said precursor of a dispersed catalyst is selected from pyrite and molybdenum sulphide or selected from molybdenum naphthenate, nickel naphthenate, vanadium naphthenate, phosphomolybdic acids, ammonium molybdates, molybdenum octoates, nickel octoate, vanadium octoate and pentacarbonyl iron. 
     
     
         15 . The process as claimed in  claim 1 , in which the quantity of dispersed catalyst in the reactor or reactors is in the range 1 ppm by weight to 10000 ppm by weight with respect to the feed.